WO2021139092A1 - Ligand compound, and functionalized metal-organic framework compound prepared by same, preparation method therefor and application thereof - Google Patents

Abstract

Disclosed are a ligand compound, and a functionalized metal-organic framework compound prepared by same, a preparation method therefor and an application thereof. The structure of the ligand compound is as shown in Formula (I); the ligand compound is used as a ligand to form a functionalized metal-organic framework compound with cadmium chloride by means of self-assembly; the functionalized metal-organic framework compound (LIFM-ZCY-1) has a higher fluorescence quantum yield and a long room-temperature phosphorescence lifetime, and has the advantages of high emission intensity and stable luminous performance; and under vacuum conditions, luminescence is still continued for a long time after an excitation light source is turned off. The LIFM-ZCY-1 does not contain mercury, and is non-toxic, non-volatile, easy to recycle, and environmentally friendly; the composite can be used for anti-counterfeiting by means of room-temperature phosphorescent characteristics and exhibits optical properties negatively correlated with oxygen content, can be prepared into a light-emitting device, an anti-counterfeiting material and/or an oxygen sensor for application, and thus has wide application value.

Description

Ligand compound and functionalized metal-organic framework compound prepared therefrom, and preparation method and application thereof Technical field

The present invention relates to the technical field of luminescent metal-organic framework materials, and more specifically, to a ligand compound, namely 9-(4-(2,6-bis(4-(1H-tetrazol-5-yl)phenyl) )Pyridin-4-yl)phenyl)-9H-carbazole, and a functionalized metal-organic framework compound prepared by self-assembly with cadmium chloride as a ligand, and a preparation method and application thereof.

Background technique

Long Persistent Luminescence (LPL) refers to the phenomenon that the material can continue to emit light for a period of time after the excitation light source is turned off. The history of afterglow luminescence can be traced back to the beginning of the 17th century, when an Italian shoemaker observed a strong afterglow from the mineral barite. The earliest research and application materials should belong to inorganic long afterglow materials. There are many natural minerals that have long afterglow luminescence characteristics in nature, and the well-known Ye Mingzhu is one of them. People often make these ores into various kinds of handicrafts, like the luminous material "luminous cup" that is common in our daily life. Inorganic long afterglow luminescence is mainly obtained by trapping charges through impurities, crystal defects or doped ions, and is generally prepared by high temperature methods such as high temperature solid phase method, sol-gel method, and combustion. The existing synthetic process of inorganic long afterglow materials is complicated and the reaction conditions are harsh; it needs to be doped with high-priced and highly toxic rare-earth materials; in addition, it requires grinding to use and is difficult to apply to flexible substrates. It is precisely because of the shortcomings of this series of inorganic long-lasting materials that limit its further development.

Compared with inorganic long-lasting materials, metal-organic long-lasting luminescent materials have advantages in optical recording, bioimaging, information storage, anti-counterfeiting systems, etc. due to their simple synthesis, low price, flexibility, easy modification of functional groups, and good biocompatibility. The high-tech field has attractive application prospects.

Metal-organic frameworks (MOFs) are a new type of organic-inorganic hybrid porous materials with clear structure, good stability, and easy modification. The metal-organic framework is a spatial arrangement of organic ligands and metal junctions in a certain pattern, and has the luminescence properties of organic matter and metal ions at the same time. The principle of luminescence can be divided into the following aspects: (1) luminescence centered on organic ligands (LC); (2) metal/cluster center luminescence (MC); (3) metal-ligands Charge transfer (MLCT, LMCT); (4) Charge transfer from ligand to metal cluster core (LMCCCT); (5) Metal-metal interaction disturbance (LMMC), etc. The metal atoms in the metal-organic framework have a heavy atom effect, which greatly accelerates the process of intersystem crossing, and has a positive effect on the phosphorescence and afterglow properties. It is expected to obtain an ideal long-lasting material. However, for the long-lasting metal-organic framework, There are still very few reports.

Summary of the invention

The purpose of the present invention is to provide a ligand compound in view of the lack of research on long-lasting metal-organic framework compounds in the prior art. The ligand compound has a novel structure and can be used as a ligand to form a functionalized metal-organic framework compound through self-assembly with cadmium chloride, and the functionalized metal-organic framework compound formed is a single material and is colorless and transparent Flake crystals have high fluorescence quantum yield and long continuous luminescence. They have the advantages of high emission intensity and stable luminescence performance. Phosphorescence intensity and lifetime are affected by oxygen content; under vacuum conditions, the excitation light source is still visible to the naked eye Red afterglow. The functionalized metal-organic framework material of the present invention does not contain mercury, is non-toxic and non-volatile, has stable properties, is easier to recycle, and is environmentally friendly.

The second object of the present invention is to provide a method for preparing the ligand compound.

The third object of the present invention is to provide the ligand compound as a raw material for use in the preparation of functionalized metal-organic framework compounds.

The fourth object of the present invention is to provide a functionalized metal-organic framework compound prepared with the ligand compound as a raw material.

The fifth object of the present invention is to provide a method for preparing the functionalized metal-organic framework compound.

The sixth object of the present invention is to provide an application of the functionalized metal-organic framework compound.

The above-mentioned objects of the present invention are achieved through the following schemes:

A ligand compound, characterized in that the structure of the ligand compound is as shown in formula (I):

The preparation method of the ligand compound is also within the protection scope of the present invention, and includes the following steps:

S1. Preparation of Intermediate 1: Under inert gas atmosphere, carbazole and 4-bromobenzaldehyde undergo a Buchwald-Hartwig reaction to obtain Intermediate 1 (ie 4-(carbazol-9-yl)benzaldehyde);

S2. Preparation of Intermediate 2: Intermediate 1, p-cyanoacetophenone and inorganic base are miscible in alcoholic organic solvent for reaction, and then ammonia water is added for reaction. After the reaction is over, the product is separated to obtain Intermediate 2 (Ie 4,4'-(4-(4-(4-(9H-carbazol-9-yl)phenyl)phenyl)pyridine-2,6-di)dibenzonitrile);

S3. Preparation of the target compound: The N-methylpyrrolidone solution in which intermediate 2 is dissolved is added to the sodium azide aqueous solution, and the reaction is refluxed at 120-150°C under stirring conditions. After the reaction is completed, the product is separated. The target compound represented by formula (I) is obtained.

Preferably, in step S1, the Buchwald-Hartwig reaction is carried out in the presence of potassium carbonate, palladium acetate and tri-tert-butyl phosphine; more preferably, the reaction process is: under an inert gas atmosphere, the carbazole, 4- Bromobenzaldehyde, potassium carbonate, palladium acetate and tri-tert-butyl phosphine are miscible in anhydrous organic solvent, heated to reflux for reaction, after the reaction is over, the product is separated to obtain Intermediate 1.

Preferably, in step S1, the ratio of carbazole, 4-bromobenzaldehyde and potassium carbonate is 12:12-16:24-36; more preferably, the ratio is 12:13.5:30.

Preferably, in step S1, the organic solvent is toluene, N,N dimethylformamide or N,N dimethylacetamide.

Preferably, in step S1, the reflux reaction time is 36 to 72 hours.

Preferably, in step S1, after the reaction is completed, the process of product separation is: the reaction solution is cooled to room temperature, filtered, the filtrate is taken, and then extracted with water and dichloromethane, the organic phase is taken, the solvent is removed, and the residue is passed through Purified by column chromatography to obtain Intermediate 1.

More preferably, in the process of product separation in step S1, in the column chromatography process, the mobile phase is petroleum ether and dichloromethane with a volume ratio of 1:1.

Preferably, in step S2, the mass ratio of intermediate 1, cyanoacetophenone and sodium hydroxide: 15-25:40:30-50; more preferably, the ratio is 20:40:40.

Preferably, in step S2, the organic base is an alkali substance commonly used in the art, such as sodium hydroxide, potassium hydroxide, and the like.

Preferably, in step S2, the alcoholic organic solvent is an alcohol with a carbon number of less than 4 commonly used in the art, such as methanol, ethanol, propanol, isopropanol, and the like.

Preferably, in step S2, after the reaction is completed, the process of product separation is as follows: the reaction solution is filtered, the filter cake is taken, and purified by column chromatography to obtain Intermediate 2.

More preferably, in the process of product separation in step S2, in the column chromatography process, the mobile phase is petroleum ether and dichloromethane with a volume ratio of 1:2.

Preferably, in step S3, the molar ratio of intermediate 2 and sodium azide is 1:5-10; more preferably, the ratio is 1:8.

Preferably, in step S3, the volume ratio of water to N-methylpyrrolidone is 1:3-7; more preferably, the ratio is 1:5.

Preferably, in step S3, the temperature of the reaction is 150°C.

Preferably, in step S3, after the reaction is finished, the process of product separation is: the reaction solution is cooled to room temperature, the mixture is acidified to pH 1 by adding HCl aqueous solution, and then filtered, the filter cake is taken, and dried to obtain the target product.

The invention also protects the application of the ligand compound in the preparation of functionalized metal-organic framework compounds.

A functionalized metal-organic framework compound, namely LIFM-ZCY-1, whose molecular formula is C ₃₇ H ₃₂ CdN ₁₀ O ₄ , is a monoclinic system, and the space group of the monoclinic system is C2/c, which is also in Within the protection scope of the present invention.

Preferably, the functionalized metal-organic framework compound uses the compound of formula (I) as a ligand, and is formed by self-assembly with cadmium chloride.

The present invention also protects the preparation method of the functionalized metal-organic framework compound. The compound of formula (I) and cadmium chloride are miscible in N,N-dimethylacetamide and ethanol aqueous solution at 80-100°C. After the reaction is completed, the product is separated to obtain the functionalized metal-organic framework compound.

Preferably, the mass ratio of the compound of formula (I) and cadmium chloride is 5-10:10.

Preferably, the mass ratio of the compound of formula (I) and cadmium chloride is 5:10.

Preferably, the mass ratio of the N,N-dimethylacetamide, ethanol and water is 1:0.5-2:0.5-2.

The invention also protects the application of the functionalized metal-organic framework compound in preparing light-emitting devices, anti-counterfeiting materials and/or oxygen sensors.

Preferably, the oxygen sensor is a multi-dimensional visualized oxygen sensor.

Compared with the prior art, the present invention has the following beneficial effects:

The ligand compound of the present invention has a novel structure and can be used as a ligand to form a functionalized metal-organic framework compound through self-assembly with cadmium chloride, and the functionalized metal-organic framework compound formed is a single material, which is not Color transparent flake crystals, with high fluorescence quantum yield and long continuous luminescence, with the advantages of high emission intensity and stable luminescence performance. The phosphorescence intensity and life span are affected by oxygen content; under vacuum conditions, it still has the advantages of turning off the excitation light source. Red afterglow visible to the naked eye. The functionalized metal-organic frame material of the present invention does not contain mercury, is non-toxic and non-volatile, has stable properties, is easier to recycle, is environmentally friendly, and can be prepared into light-emitting devices, anti-counterfeiting materials and/or oxygen sensors For application, it has a wide range of application value.

Description of the drawings

Figure 1 is the ligand compound 9-(4-(2,6-bis(4-(1H-tetrazol-5-yl)phenyl)pyridin-4-yl)phenyl)-9H- prepared in Example 1. Proton NMR spectrum of carbazole.

2 is a schematic diagram of the chemical structure of LIFM-ZCY-1 prepared in Example 1.

Fig. 3 is a fluorescence excitation and emission graph of LIFM-ZCY-1 prepared in Example 1 under excitation at a wavelength of 365 nm.

Figure 4 shows the fluorescence emission graphs and CIE coordinate graphs of LIFM-ZCY-1 prepared in Example 1 at different temperatures under excitation at a wavelength of 365 nm.

Fig. 5 is a graph showing the steady-state and retardation spectra of LIFM-ZCY-1 prepared in Example 1 and the heated sample LIFM-ZCY-1-heated under excitation at a wavelength of 365 nm, and lifetime diagrams of emission at a wavelength of 560 nm.

Fig. 6 shows the fluorescence spectrum and lifetime decay curve of LIFM-ZCY-1 prepared in Example 1 under excitation at 365 nm wavelength under different oxygen content.

Fig. 7 is a schematic diagram of the application of LIFM-ZCY-1 prepared in Example 1 in anti-counterfeiting.

Detailed ways

The present invention will be further elaborated below in conjunction with specific embodiments, which are only used to explain the present invention and not used to limit the scope of the present invention. The test methods used in the following examples are conventional methods unless otherwise specified; the materials and reagents used, unless otherwise specified, are commercially available reagents and materials.

All the analytical reagents used in the following examples were purchased from Innochem and can be used without further purification.

The applied instrument is: the infrared data is collected using the Nicolet/Nexus-670 Fourier infrared spectrometer in the ^{range of 4000-400cm -1} using the potassium bromide tablet method.

The samples were compressed using a Specac small tablet press.

Powder X-ray diffraction (PXRD) was measured using a Rigaku SmartLab diffractometer (Bragg-Brentano geometry, cu kα1 radiation, λ=1.54056A).

Thermogravimetric analysis (TGA) was performed on the NETZSCH TG209 system under nitrogen and 1atm pressure at ^{a heating rate of 10℃·min -1.}

^{The 1} HNMR spectrum was obtained with a JEOL EX270 spectrometer (400MHz) instrument.

A Shimadzu UV-2450 spectrophotometer was used to record the ultraviolet-visible absorption spectrum.

The fluorescence microscope picture was obtained under a 365nm ultraviolet lamp.

The fluorescence spectrum was measured by the Edinburgh FLS 980 spectrometer.

The fluorescence quantum yield data was measured on the Hamamatsu C9920-02G absolute fluorescence quantum yield measurement system.

The Astrella/OperA-Solo femtosecond laser was used to obtain the two-photon excitation fluorescence spectrum.

Example 1 Preparation of functionalized metal-organic framework compound LIFM-ZCY-1

A functionalized metal-organic framework compound LIFM-ZCY-1, composed of 9-(4-(2,6-bis(4-(1H-tetrazol-5-yl)phenyl)pyridin-4-yl)benzene (Base)-9H-carbazole is a ligand, formed by self-assembly of chromium chloride dihydrate.

The specific preparation process is:

The preparation process of 9-(4-(2,6-bis(4-(1H-tetrazol-5-yl)phenyl)pyridin-4-yl)phenyl)-9H-carbazole is:

S1. Preparation of 4-(carbazol-9-yl)benzaldehyde (Intermediate 1):

Combine carbazole (2.0g, 12mmol), 4-bromobenzaldehyde (2.5g, 13.5mmol), potassium carbonate (4.15g, 30mmol), palladium acetate (0.2g, 1.0mmol), and tri-tert-butyl phosphine (0.3 mL) was dissolved in 20 mL of anhydrous toluene under a nitrogen atmosphere and refluxed for 48 hours. After the reaction, it was cooled to room temperature, filtered, and the filtrate was taken. The filtrate was extracted with water and dichloromethane, and the organic phase was taken. After removing the solvent using a rotary evaporator, the residue was purified by column chromatography (petroleum ether/CH ₂ Cl ₂ , V/V=1:1) to obtain 2.3 g of white solid (yield 71%).

S2. 4,4'-(4-(4-(4-(9H-carbazol-9-yl)phenyl)phenyl)pyridine-2,6-bis)dibenzonitrile (intermediate) 2) Preparation:

At room temperature, p-cyanoacetophenone (5.8g, 40mmol), 4-(carbazol-9-yl)benzaldehyde (5.42g, 20mmol) and sodium hydroxide (1.6g, 40mmol) in 200mL ethanol solution After stirring for about 15 hours, add 80 mL of ammonia water and stir for another 24 hours at room temperature. Filter, take the filter cake, and purify the residue by column chromatography (petroleum ether/dichloromethane, V/V=1:2) to obtain 4.0 g of the target product as a pale yellow solid with a yield of 38%;

S3. Preparation of ligand 9-(4-(2,6-bis(4-(1H-tetrazol-5-yl)phenyl)pyridin-4-yl)phenyl)-9H-carbazole:

To a 25 mL round bottom flask was added sodium azide (1.12 g, 16 mmol) and 2 mL water. Dissolve 4,4′-(4-(4-(4-(9H-carbazol-9-yl)phenyl)phenyl)pyridine-2,6-di)dibenzonitrile (2mmol) in 10mL N -Methylpyrrolidone, pour into the aqueous solution of sodium azide. The reaction mixture was refluxed for 24 hours at a high temperature of 150°C and vigorous stirring. After the reaction was completed, the mixture was cooled to room temperature, and the mixture was acidified to pH 1 with aqueous HCl solution (1M). Under vigorous stirring, precipitation appeared. The filter cake was filtered and dried to obtain a white solid product.

The hydrogen nuclear magnetic resonance spectrum of ligand 9-(4-(2,6-bis(4-(1H-tetrazol-5-yl)phenyl)pyridin-4-yl)phenyl)-9H-carbazole is shown as As shown in Figure 1, its structure is shown in (Ⅰ):

The self-assembly process of 9-(4-(2,6-bis(4-(1H-tetrazol-5-yl)phenyl)pyridin-4-yl)phenyl)-9H-carbazole and cadmium chloride: Weigh the product 9-(4-(2,6-bis(4-(1H-tetrazol-5-yl)phenyl)pyridin-4-yl)phenyl)-9H-carbazole 5mg in step S3 respectively , 10mg of cadmium chloride dihydrate in a 10ml glass vial, add 1ml N,N-dimethylacetamide, 1ml water, 1ml ethanol to dissolve it, then seal the glass bottle and place it in a 90°C oven After two days of reaction, colorless and transparent flake crystals are obtained, which is the target product metal-organic framework compound LIFM-ZCY-1.

Example 2 Determination of the crystal structure of the functionalized metal-organic framework compound LIFM-ZCY-1

With copper target

On the Rigaku-Oxford supernova X-ray diffractometer system, the single crystal X-ray diffraction data of LIFM-ZCY-1 was collected at 50kV and 0.80mA.

The structure is solved by the direct method and refined by the full matrix least square method using the SHELXL-2014 program package. All hydrogen atoms are obtained by the theoretical hydrogenation method and refined along the anisotropy direction, using the isor command to fix the frame. The crystallographic data of LIFM-ZCY-1 is shown in Table 1, and the topological structure is shown in Figure 2.

Table 1 shows the crystallographic data of the metal-organic framework complex LIFM-ZCY-1

Among them, Figure 2 is the crystal structure diagram of LIFM-ZCY-1, a) LIFM-ZCY-1 asymmetric unit structure; b) LIFM-ZCY-1 one-dimensional chain structure; c) LIFM-ZCY-1 Chained stacked graph.

Example 3 Determination of the fluorescence properties of LIFM-ZCY-1

The solid powder of LIFM-ZCY-1 shows blue fluorescence under the excitation light of 365nm wavelength, the maximum emission peak is around 460nm, and the maximum excitation peak is around 370nm, as shown in Figure 3.

At the same time, LIFM-ZCY-1 showed a thermochromic effect, as shown in Figure 4. When the temperature gradually increased from 300K to 460K, a new peak around 560nm appeared behind the original fluorescence peak around 460nm. In addition, the position of this peak will red-shift as the temperature rises. When the temperature exceeds 460K, the new peak will no longer be red-shifted at about 600nm. The light-emitting color of LIFM-ZCY-1 also changes from blue at 300K to orange-red at 460K as the temperature rises, and the CIE coordinates change from (0.21, 0.19) to (0.54, 0.42). After LIFM-ZCY-1 is heated and returned to room temperature, the sample still maintains orange-red luminescence. The heated sample is named LIFM-ZCY-1-heated.

Example 4 Determination of Room Temperature Phosphorescence Properties of LIFM-ZCY-1

Through optical testing of LIFM-ZCY-1 and LIFM-ZCY-1-heated solid powder after heating, the optical properties of LIFM-ZCY-1 and LIFM-ZCY-1-heated were obtained respectively (Figure 5).

It can be seen from Figure 5 that the emission peak of LIFM-ZCY-1 at 460nm is a nanosecond lifetime and is a fluorescence peak. From the phosphorescence spectrum (Delay) of LIFM-ZCY-1, it can be seen that its phosphorescence peak is located at 560nm, and the phosphorescence lifetime is as high as 5.57ms. The steady-state fluorescence spectrum (Prompt) of LIFM-ZCY-1-heated shows two emission peaks located at 460nm and 600nm respectively, and the emission peak at 460nm is attributed to the ligand-based fluorescence emission. Through the delay test of LIFM-ZCY-1-heated, it is found that the phosphorescence spectrum is located at 620nm, and the phosphorescence lifetime is as long as 10 milliseconds. It can be inferred that the 600nm peak in the steady-state fluorescence spectrum of LIFM-ZCY-1-heated is a combination of excimer luminescence and triplet phosphorescence caused by stacking. In addition, it is found from the test results that the life of LIFM-ZCY-1 under vacuum is as long as 18 milliseconds, which is much longer than the phosphorescence life under air conditions, indicating that its life is seriously affected by oxygen. At the same time, this embodiment tested the phosphorescence lifetime of the LIFM-ZCY-1-heated after heating, and found that its lifetime was as long as 30 milliseconds. In addition, it was found that under vacuum conditions, with the excitation light source turned off, the LIFM-ZCY-1-heated sample can emit red afterglow visible to the naked eye.

Example 5 LIFM-ZCY-1 optical property test under different oxygen content

Due to the unique long room temperature phosphorescence properties of LIFM-ZCY-1 and the long lifetime under vacuum conditions, it is speculated that the room temperature phosphorescence intensity and lifetime of LFM-ZCY-1 will vary with the oxygen content in the environment. Therefore, the steady-state spectra and lifetime of LIFM-ZCY-1-heated after heating under different oxygen content atmospheres were tested, and the measured results are shown in Figure 6.

The experimental results show that under 365nm excitation, the peak intensity of LIFM-ZCY-1-heated at 600nm is obviously quenched with the increase of oxygen concentration. Due to the luminescence of 600nm, the CIE coordinates have changed from (0.41, 0.25) in vacuum to (0.32, 0.20) in pure oxygen. However, even under pure oxygen, the 600nm peak will not completely disappear. The LIFM-ZCY-1-heated sample life is only 5 milliseconds after heating under pure oxygen conditions, while it can be as long as 30 milliseconds under vacuum conditions. In addition, the phosphorescence lifetime at 620nm shows different quenching rates in high oxygen content (>300mbar) and low oxygen content (<300mbar), and shows better sensitivity at low oxygen content, which indicates that the quenching process includes Multiple quenching mechanisms, including the quenching of 620nm room temperature phosphorescence by oxygen and the quenching of excimer luminescence.

LIFM-ZCY-1 has excellent luminescence properties and stable optical properties, and has the potential to be used in illumination, optical coding and information transmission. At the same time, its high sensitivity to oxygen can be applied to oxygen sensors. Because of its luminous intensity, luminous color, luminous lifetime, and afterglow time, it responds to oxygen in varying degrees, so it can be used as a multi-dimensional visual oxygen sensor.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. For those of ordinary skill in the art, they can also make decisions based on the above descriptions and ideas. For other changes or changes in different forms, it is not necessary and impossible to enumerate all the implementation methods here. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims (10)

1. A ligand compound, characterized in that the structure of the ligand compound is as shown in formula (I):

   
2. The preparation method of the ligand compound according to claim 1, characterized in that it comprises the following steps:

   S1. Preparation of Intermediate 1: Under an inert gas atmosphere, carbazole and 4-bromobenzaldehyde undergo a Buchwald-Hartwig reaction to obtain Intermediate 1;

   S2. Preparation of Intermediate 2: Intermediate 1, p-cyanoacetophenone and inorganic base are miscible in alcoholic organic solvent for reaction, and then ammonia water is added for reaction. After the reaction is over, the product is separated to obtain Intermediate 2 ；

   S3. Preparation of the target compound: The N-methylpyrrolidone solution in which intermediate 2 is dissolved is added to the sodium azide aqueous solution, and the reaction is refluxed at 120-150°C under stirring conditions. After the reaction is completed, the product is separated. The target compound represented by formula (I) is obtained.
3. The use of the ligand compound of claim 1 in the preparation of a functionalized metal-organic framework compound.
4. A functionalized metal-organic framework compound, characterized in that its molecular formula is C ₃₇ H ₃₂ CdN ₁₀ O ₄ , is a monoclinic system, and the space group of the monoclinic system is C2/c.
5. The functionalized metal-organic framework compound according to claim 4, wherein the functionalized metal-organic framework compound is formed by self-assembly with the compound of formula (I) as a ligand.
6. The preparation method of the functionalized metal-organic framework compound according to claim 4 or 5, characterized in that the compound of formula (I) and cadmium chloride are miscible in N,N-dimethylacetamide and ethanol aqueous solution. The reaction is sealed at 80-100° C., and after the reaction is completed, the product is separated to obtain the functionalized metal-organic framework compound.
7. The method for preparing a functionalized metal-organic framework compound according to claim 6, wherein the mass ratio of the compound of formula (I) and cadmium chloride is 5-10:10.
8. The method for preparing a functionalized metal-organic framework compound according to claim 7, wherein the mass ratio of the compound of formula (I) and cadmium chloride is 5:10.
9. The method for preparing a functionalized metal-organic framework compound according to claim 6, wherein the mass ratio of the N,N-dimethylacetamide, ethanol and water is 1:0.5-2:0.5-2.
10. Application of the functionalized metal-organic framework compound of claim 1 in the preparation of light-emitting devices, anti-counterfeiting materials and/or oxygen sensors.

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